EP2648844A1 - Novel oxide material and synthesis by fluoride/chloride anion promoted exfoliation - Google Patents
Novel oxide material and synthesis by fluoride/chloride anion promoted exfoliationInfo
- Publication number
- EP2648844A1 EP2648844A1 EP11846722.4A EP11846722A EP2648844A1 EP 2648844 A1 EP2648844 A1 EP 2648844A1 EP 11846722 A EP11846722 A EP 11846722A EP 2648844 A1 EP2648844 A1 EP 2648844A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ucb
- oxide material
- delaminated
- aqueous mixture
- fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 106
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 35
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 title abstract description 42
- 238000003786 synthesis reaction Methods 0.000 title abstract description 40
- 238000004299 exfoliation Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 87
- 230000032798 delamination Effects 0.000 claims abstract description 72
- 239000012690 zeolite precursor Substances 0.000 claims abstract description 52
- -1 chloride anions Chemical class 0.000 claims abstract description 41
- 238000000527 sonication Methods 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000000203 mixture Chemical group 0.000 claims description 74
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical class [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 40
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 21
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Chemical group 0.000 claims description 5
- 230000036961 partial effect Effects 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 42
- 239000007864 aqueous solution Substances 0.000 abstract description 17
- 230000020477 pH reduction Effects 0.000 abstract description 13
- 239000002243 precursor Substances 0.000 abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 56
- 239000010457 zeolite Substances 0.000 description 45
- 239000000047 product Substances 0.000 description 41
- 229910021536 Zeolite Inorganic materials 0.000 description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 238000000634 powder X-ray diffraction Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 12
- 238000001144 powder X-ray diffraction data Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000008961 swelling Effects 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 238000004375 physisorption Methods 0.000 description 7
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000004627 transmission electron microscopy Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 238000005280 amorphization Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229910001657 ferrierite group Inorganic materials 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 3
- DICGYDRHQMUZEA-UHFFFAOYSA-N 2,3-bis(2-methylpropyl)-1h-imidazol-3-ium;hydroxide Chemical compound [OH-].CC(C)CC=1NC=C[N+]=1CC(C)C DICGYDRHQMUZEA-UHFFFAOYSA-N 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002459 porosimetry Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010414 supernatant solution Substances 0.000 description 2
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical compound C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 description 1
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 1
- UWKQJZCTQGMHKD-UHFFFAOYSA-N 2,6-di-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=N1 UWKQJZCTQGMHKD-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QXNDZONIWRINJR-UHFFFAOYSA-N azocane Chemical compound C1CCCNCCC1 QXNDZONIWRINJR-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- VXVVUHQULXCUPF-UHFFFAOYSA-N cycloheptanamine Chemical compound NC1CCCCCC1 VXVVUHQULXCUPF-UHFFFAOYSA-N 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000000449 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Definitions
- new oxide materials consisting of delaminated layered zeolite precursors and a method for synthesizing the materials under mild conditions. More specifically, provided is the synthesis of delaminated layered zeolite precursor materials such as UCB-1 to UCB-6 by fluoride/chloride anion-promoted exfoliation.
- ITQ-2 in particular represents the first example of such a material, and consists of micropores derived from the zeolite precursor material, MCM- 22(P), which are imbedded within thin and accessible sheets. See, for example, U.S. Patent No. 6,231,751. These micropores enable shape-selective catalysis.
- Other delaminated zeolite materials include ITQ-6 synthesized by delamination of PREFER, and ITQ-18, synthesized by delamination of Nu-6(1).
- An objective of the present invention is to provide a flexible process insofar as it can be used at milder pH values, either in organic solvents or in aqueous solution, and either with or without sonication. This flexibility in process conditions is not possible to achieve with the prior art.
- novel delaminated zeolite precursor materials prepared by fluoride/chlorine anion-promoted exfoliation.
- the oxide material prepared by at least partial delamination of a layered zeolite precursor is essentially devoid of an amorphous silica phase. This is achieved through the use of chloride and fluoride anion exfoliation.
- the avoidance of the amorphous phase in the oxide materials of the present invention also preserves more integrity of the two-dimensional zeolite layers, as characterized, for example, by a more intense sharp peak in the 20-30 29/degrees range of their X-ray diffraction patterns compared to prior art delaminated layered zeolite materials such as ITQ-2, lack of resonances attributable to Si(OH) 2 - Q 2 silicon - via 29 Si MAS NMR spectroscopy, and lack of amorphous phase via transmission electron microscopy.
- the method of preparing the delaminated layered zeolite precursor material comprises preparing an aqueous mixture of chloride and fluoride anions with a layered zeolite precursor material to be delaminated.
- the aqueous mixture is maintained at a pH of 12 or less, e.g., around 9, generally at a temperature in the range of about 5-150°C to effect the desired delamination.
- An oxide material such as UCB-1 is then recovered after acidification and centrifugation, and can be obtained in yields exceeding 90 wt.%.
- the use of milder conditions, especially pH, during the synthesis using an aqueous solution substantially avoids the creation of an amorphous phase, whereas the obviation of sonication is a practical cost-effective advantage of the synthesis.
- the method of preparing the delaminated layered zeolite precursor comprises preparing a non-aqueous mixture of chloride and fluoride anions with a layered zeolite material to be delaminated.
- the mixture is heated at a temperature in the range of about 5-150°C to effect the desired delamination.
- the non-aqueous mixture generally comprises an organic solvent such as dimethyl formamide (DMF).
- An oxide material such as UCB-2 is then recovered after acification and filtration, or, alternatively, an oxide material such as UCB-3 is then recovered after deionized water wash and filtration.
- the method of preparing the delaminated layered zeolite precursor comprises preparing a non-aqueous mixture, e.g., using an organic solvent such as dimethyl formamide, of chloride and fluoride anions with a layered zeolite material to be delaminated. After heating the mixture at a temperature in the range of from about 5-150°C to affect the desired delamination, the mixture is subjected to sonication and filtration. An oxide material such as UCB-4, UCB-5 or UCB-6 is then recovered.
- an organic solvent such as dimethyl formamide
- the present process permits one to prepare a delaminated zeolite precursor material by using a combination of chloride and fluoride anions, e.g., from a combination of alkylammonium fluoride and chloride surfactants.
- the process avoids the creation of an amorphous silica phase.
- the process permits milder conditions of pH than have heretofore been possible.
- the pH can be less than 12, and essentially avoids the creation of an amorphous silica phase.
- delamination of a layered zeolite precursor material is achieved to provide a stable product, e.g., UCB-1.
- the process can also be performed in a non-aqueous mixture, with which sonication can be used or not used.
- Stable products such as UCB-2, UCB-3, UCB-4, UCB-5 and UCB-6 are achieved.
- the products themselves are novel as they demonstrate unique morphology and high structural integrity.
- Figure 1 shows a powder x-ray diffraction pattern characterizing MCM-22(P) (Si:Al ratio of 50) delaminated in the absence of chloride;
- Figure 2 shows a powder x-ray diffraction pattern characterizing MCM-22(P) (Si:Al ratio of 50) delaminated in the absence of fluoride;
- Figure 3 is a 19 F MAS NMR spectrum characterizing as-made UCB-1 ;
- Figure 4 shows a powder x-ray diffraction pattern characterizing MCM-22 after treatment under the same conditions used to synthesize UCB-1
- Figure 5 shows a powder x-ray diffraction pattern characterizing MCM-22 after treatment under the same conditions used to synthesize ITQ-2 zeolite.
- Figure 6 shows 29 Si MAS NMR spectra characterizing (A) MCM-22(P), (B) as-made ITQ-2; and (C) as-made UCB-1.
- Figure 7 shows powder x-ray diffraction patterns characterization (A) MCM- 22(P); (B) as-made ITQ-2 zeolite; and (C) as-made UCB-1.
- Figure 8 shows 2 adsorption isotherms characterizing the following materials:
- Figure 9 shows cumulative pore volumes characterizing the following samples:
- ITQ-2 zeolite (2) MCM-22 zeolite; (3) UCB-1.
- Figure 10 are TEM images characterizing (A) and (B) MCM-22(P) and (C) and (D) UCB-1.
- Figure 12 shows the powder X-ray diffraction patterns characterizing (A) ERB-1 and (B) the delaminated product after delamination by the fluoride/chloride method of the present process.
- Figure 13 is a TEM image characterizing as-made UCB-1, with the arrows indicating single-layers.
- Figures 14 and 15 show 2 adsorption isotherms and an indication of pore size.
- Figure 16 shows a scanning electron microscopy image characterizing PREFER.
- Figure 17 shows solid-state 27 A1 MAS NMR spectra characterizing as-made UCB-2.
- Figure 18 shows powder XRD patterns characterizing the following materials:
- Figure 19 shows powder XRD patterns characterizing (a) PREFER and (b) as- made UCB-3.
- Figure 20 shows argon gas adsorption characterizing ( ⁇ ) calcined PREFER (ferrierite), and (s) calcined UCB-3 in a semi-logarithmic scale.
- the inset shows the same data in a linear scale.
- Figure 21 shows powder XRD patterns characterizing (a) PREFER and (b) as- made UCB-4.
- Figure 22 shows argon gas adsorption isotherms characterizing ( ⁇ ) calcined PREFER (ferrierite), and (») calcined UCB-4 in a semi-logarithmic scale.
- the inset shows the same data in a linear scale.
- the data for calcined PREFER is shown as a comparison.
- Figure 23 shows powder XRD patterns characterizing (a) as-made Al-SSZ-70 and
- Figure 24 shows argon gas adsorption isotherms characterizing ( ⁇ ) calcined Al- SSZ-70 and ( 4 ) calcined UCB-5 in a semi-logarithmic scale.
- the inset shows the same data in a linear scale.
- Figure 25 shows powder XRD patterns characterizing (a) as-made B-SSZ-70 and (b) as-made UCB-6.
- Figure 26 shows argon gas adsorption characterizing (A) calcined B-SSZ-70 and (*) calcined UCB-6 in a semi-logarithmic scale.
- the inset shows the same data in a linear scale.
- Figure 27 shows chemisorbed amounts of base molecules onto acid sites in calcined material UCB- 1.
- the present method involves halide anion delamination of a layered zeolite precursor material to provide a novel oxide material.
- An aqueous mixture or an organic solvent mixture of chloride and fluoride anions is used in affecting the delamination.
- Bromide anion can also be present.
- the mixtures are maintained at a temperature in the range of from 5 - 150°C for a length of time sufficient to effect the desired delamination, e.g., for 30 minutes to one month.
- the mixture can then be subjected to sonication, or the process can be completed in the absence of sonication.
- the oxide product is recovered, often using acidification and/or centrifugation.
- the recovered oxide products recovered by the present halide anion delamination process are novel oxide products having unique morphology and high structural integrity.
- the present process allows one to prepare a delaminated layered zeolite precursor material efficiently and under milder conditions than has heretofore been known.
- the synthesis substantially avoids the creation of an amorphous phase, and can circumvent the need for sonication.
- a zeolite is a crystalline three-dimensional assembly of tetrahedral atoms, each of which is surrounded by four oxygen atoms as ligands, so as to form T0 4 units where T represents a tetrahedral atom and can be, but is not limited to, silicon, germanium, vanadium, titanium, tin, aluminum, boron, iron, chromium, gallium, cerium, lanthanum, samarium, phosphorous, and a mixture thereof. These T0 4 units are interconnected through their corners. Zeolites can be but are not limited to aluminosilicates, aluminophosphates, heteroatom-substituted materials.
- a layered zeolite precursor material consists of two- dimensional zeolitic sheets that are interconnected via either non-covalent (e.g., hydrogen bonding) and/or covalent bonds, which when calcined lead to a three-dimensional zeolite.
- the novel oxide product is prepared at a pH less than 12, e.g., about 9, and maintained at a temperature in the range of 5-150°C for a length of time sufficient to effect the desired delamination.
- the oxide product is then recovered, e.g., by acidification to a pH of about 2 followed by centrifugation.
- the mixture is also maintained at a temperature in the range of from 5 - 150°C to effect desired delamination.
- the organic solvent can be any suitable organic solvent, which swells the starting material such as dimethyl formamide (DMF).
- DMF dimethyl formamide
- the delaminated product can then be recovered from the mixture. Generally, acidification is used to recover the product. Sonication prior to recovery need not be employed, but sonication can be employed in the process if desired.
- the oxide product obtained can comprise oxides of the formula XO2 and Y2O 3 , wherein X represents a tetravalent element and Y represents a trivalent element, with the atomic ratio of X to Y being greater than 3.
- X is silicon, germanium, vanadium, titanium, tin, or a mixture thereof
- Y is selected from the group consisting of aluminum, boron, iron, chromium, titanium, gallium, cerium, lanthanum, samarium, and a mixture thereof. See “Framework-substituted lanthanide MCM-22 zeolite: synthesis and characterization", J. Am. Chem. Soc, 2010, 132, pp.
- X is silicon and Y is aluminum.
- the atomic ratio of X to Y is also often less than 200, or less than 100.
- the oxide product may contain pentavalent phosphorous as well as the elements defined above (e.g., as in an aluminophosphate material).
- the layered zeolite precursors to be delaminated in accordance with the present process can be any layered zeolite material.
- the ultimate product will depend upon the starting material and the particular process steps used in the synthesis.
- suitable layered zeolite precursor materials include MCM-22 (P), SSZ-25, ERB-1, PREFER, SSZ-70 (e.g., Al-SSZ-70 or B-SSZ-70) and Nu-6 (1).
- MCM-22 (P) the novel oxide product UCB-1 is obtained.
- the chloride and fluoride anions can be obtained from any source of the anions. Any compound which will provide the anions in aqueous solution can be used.
- the cation is not important. Providing the fluoride and chloride anions is important.
- the cations can be any cation, with the use of alkylammonium cations being suitable in one embodiment.
- the alkyl group of such a cation can be any length, and in one embodiment ranges from 1-20 carbons. Tetrabutylammonium cations in particular have been found useful.
- the molar ratio of chloride to fluoride anions can be 100 or less, generally from 100: 1 to 1 : 100. In one embodiment, the ratio can range from 50: 1 to 1 :50.
- the pH used in the present synthesis when an aqueous mixture is used is lower than that generally used in delamination synthesis.
- the pH is generally 12 or less, but can be any pH which does not amorphasize the silica in the zeolite to create an amorphous silica phase.
- a pH of 12 or less generally accomplishes this task and thereby allows one to obtain a delaminated layered zeolite precursor material substantially without an amorphous phase.
- the pH is 11 or less, and even 10 or less, with a pH of about 9 or less also being quite advantageous.
- a pH of approximately 9 is typically used in fluoride- mediated synthesis of zeolites - which otherwise require high pH (above 12). See Corma et al, "Synthesis in fluoride media and characterisation of aluminosilicate zeolite beta", Journal of Materials Chemistry, 1998, 8, pp. 2137 - 2145.
- the temperature used in the process for either the aqueous or non-aqueous mixture can range widely. In general a temperature for the aqueous solution of from 5-150°C is suitable. In another embodiment, the temperature can range from 50-100°C.
- the length of time the zeolite is allowed to swell, and delaminate, in the aqueous solution can vary greatly. Generally, the time can vary from 30 minutes to one month. In one embodiment, the time ranges from 2 hours to 50 hours. In another embodiment, the time can range from 5 to 20 hours prior to collection of the product.
- the oxide product is collected using conventional techniques such as centrifugation.
- An acid treatment step can be employed prior to centrifugation, and may be conveniently conducted by contacting the swollen or partially delaminated layered zeolite precursor material with a strong acid, e.g., a mineral acid such as hydrochloric acid or nitric acid, at low pH, e.g., pH 2. Collection of the resulting oxide material product can be performed by centrifugation.
- the oxide product obtained by the present process depends on the starting material.
- any layered zeolite material can be used as a precursor in the present delamination process.
- MCM-22 can be used as the precursor layered zeolite material, hereinafter designated as MCM-22(P).
- MCM-22(P) can be used as the precursor layered zeolite material, hereinafter designated as MCM-22(P).
- MCM-22(P) Using the preset fluoride/chloride anion promoted exfoliation procedure on MCM-22(P) results in a novel UCB-1 product. Characterization of UCB-1 product by powder x-ray diffraction, transmission electron microscopy, and nitrogen physiorption at 77K (-194°C) indicates the same degree of delamination as for previously reported ITQ-2.
- UCB-1 is comprised of a higher degree of structural integrity and no detectable formation of amorphous silica phase.
- Powder X-ray diffraction patterns characterizing (A) MCM-22 (P), (B) ITQ-2 zeolite, and (C) new material UCB-1 are shown in Figure 7.
- the powder X-ray diffraction pattern characterizing the synthesized MCM-22 (P) ( Figure 7, pattern A) matches the literature data, showing the 001 and 002 diffraction peaks at 3.3 and 6.7°, respectively. These peaks represent the lamellar structure of MCM-22 (P). Delamination of MCM-22 (P) by the method described in U.S. Patent No. 6,231,751 leads to a significant decrease of all peaks characteristic of lamellar structure of MCM-22 (P) ( Figure 7, pattern B), in agreement with the literature results for characterizing ITQ-2 zeolite.
- the PXRD of the dried UCB-1 product demonstrates a powder pattern similar to that previously reported for ITQ-2 zeolite.
- the pattern at Figure 7C is characteristic of UCB- 1.
- the 001 and 002 peaks are significantly diminished in intensity; however, the 310 peak has a stronger intensity than for material ITQ-2. This suggests a greater degree of long-range order in the direction parallel to the sheet for the material synthesized by the present fluoride/chloride delamination method.
- the relative intensity ratio of the local maximum of X-ray diffraction peak in the range of 6-10 29/degrees to that of 20-30 29/degrees can be 0.50 or less.
- Zeolite TON consists of only 10 MR channels and shows pore filling of these channels starting at a relative pressure P/P o of 10 "7 .
- Zeolite USY consists of 12 MR windows and large ( ⁇ 13 A) supercages, and shows pore filling of these pores at a relative pressure in the range of 10 " 5 ⁇ P/P 0 ⁇ 10 "4 .
- the isotherm for UCB-1 in Figure 8 essentially overlaps the isotherm for ITQ-2 in the region 10 "7 ⁇ P/P 0 ⁇ 10 "4 , which indicates that both materials have similar amounts of 10 MR and 12 MR pores. This requires that the degree of delamination for both materials is similar.
- ITQ-2 consists of larger micropores and mesopores, which are absent in UCB-1. Because of delamination, UCB-1 has a larger pore volume of large pores than MCM-22 as shown in Table 1 below (0.36 cm 3 /g for UCB-1 vs. 0.22 cm 3 /g for MCM-22). However, ITQ-2 has a significantly larger volume than UCB-1 (0.67 cmVg vs. 0.36 cmVg) because of mesopore formation by amorphization. See, Figures 14 and 15, which show the 2 adsorption isotherms with an indication of pore size.
- Pore volume of MCM-22, UCB-1, and ITQ-2 determined from N2 gas adsorption data
- TEM of UCB-1 demonstrates this macroporosity, which is formed between stacks of sheets, and shows the absence of mesoporosity that is evident in ITQ-2.
- the MCM-22 precursor may be prepared by methods known in the art, e.g., from a reaction mixture containing an oxide of a tetravalent element (X), e.g., silicon, an oxide of a trivalent element (Y), e.g., aluminum, an organic directing agent (organic template), water and, optionally, sources of alkali or alkaline earth metal (M), e.g., sodium or potassium cation.
- X tetravalent element
- Y oxide of a trivalent element
- organic template organic directing agent
- M alkali or alkaline earth metal
- organic templates examples include heterocyclic imines (e.g., hexamethyleneimine, 1 ,4-diazacycloheptane and azacyclooctane), cycloaklyl amines (e.g., aminocyclopentane, aminocyclohexane and aminocycloheptane), adamantane quarternary ammonium ions (e.g., N,N,N-trimethyl-l-adamantanammonium ions and N,N,N-trimethyl-2- adamantanammonium ions), and mixtures of N,N,N-trimethyl-l-adamantanammonium ions or N,N,N-trimethyl-2-adamantanammonium ions with either hexamethyleneimine or dipropylamine.
- heterocyclic imines e.g., hexamethyleneimine, 1 ,4-diazacycloheptane and azacyclooctane
- the reaction mixture is allowed to crystallize at a temperature in the range from 80 to 225°C for a period of 1 to 60 days.
- the crystals that form are separated from the reaction mixture, washed thoroughly with water and dried to yield the MCM-22 precursor.
- delamination of MCM-22 (P) by the present method can be conducted using an aqueous mixture of cetyltrimethylammonium bromide,
- TEM images of MCM-22 show lamellar assemblies consisting of rectilinear sheets, see Figures 10A and 10B.
- TEM images of UCB-1 clearly show curved layers ( Figures IOC and 10D) which lack long-range order, as well as single layers of 2.5 nm thickness ( Figure 13).
- the method used to synthesize UCB-1 can also be used to delaminate layered zeolite precursor materials containing boron. This has never been reported using the conventional method based on high pH presumably because it leads to degradation of the borosilicate framework.
- as-made ERB-1 zeolite which contains boron instead of aluminum, can essentially be delaminated by the present method as indicated by significantly decreased 001 (3.4° ⁇ 26 A) and 002 (6.8° ⁇ 13 A) peaks of the sample used in the present method. See Figure 12, pattern B is the product and pattern A is the ERB-1 starting sample.
- the present fluoride/chloride method successfully delaminates MCM-22 (P) at a pH of 9 in aqueous solution.
- the method is also able to successfully delaminate lower Si:Al ratio precursors as well as boron-containing layered zeolite precursors.
- the present method can readily be generalized to materials with varying silicon to aluminum ratios as well as a range of layered zeolite precursors.
- Novel oxide products UCB-2, UCB-3, UCB-4, UCB-5 and UCB-6 can also be prepared using the present halide anion delamination process.
- the starting material for preparing the products is generally a layered zeolite precursor consisting of either PREFER or an SSZ-70, i.e., either Al-SSZ-70 or B-SSZ-70.
- the synthesis of these oxide products involves the use of a non-aqueous solution comprising an organic solvent. DMF is such a suitable solvent.
- UCB-2 which is comprised of delaminated PREFER, is a precursor to ferrierite zeolite that contains 8 and 10 MR microchannels.
- the process involves the present process of halide anion delamination, and uses a non-aqueous solution for delamination. DMF has been found to be suitable as the organic solvent for the process.
- the zeolite products can be used as catalysts in organic conversion processes such as catalytic cracking or alkylation reactions.
- the zeolite materials can be used alone, or with other catalysts, and can be supported or used in bulk. They can also be used as a support for large catalysts that would otherwise be unable to penetrate the interior microporosity of a three-dimensional zeolitic material.
- the present process is advantageously flexible insofar as it can be used at milder pH values, either in organic solvents or in aqueous solution, and either with or without sonication. Such flexibility is not possible with prior art processes.
- Fumed silica (Sigma Aldrich, 3.54 g) was added to an aqueous solution containing sodium hydroxide (EMD Chemicals, 97%, 0.372 g), hexamethyleneimine (Sigma Aldrich, 99%, 2.87 g), and sodium aluminate (Riedel-de Haen, 0.108 g) in deionized water (46.6 g) under vigorously stirring. After stirring the mixture for 6 h, the gel was divided into four portions and each portion was loaded into a Teflon-lined Parr reactor (23 mL). Each reactor was tightly sealed and heated in a convection oven at 408 K for 11 days with tumbling of the reactor. After 11 days of heating, the reactors were cooled down to room temperature, and the product was separated by centrifuge. The separated product was washed with deionized water thoroughly, and finally dried at 313 K overnight.
- EMD Chemicals 97%, 0.372 g
- hexamethyleneimine Sigma Aldrich
- MCM-22 (P) Delamination of MCM-22 (P) by the Conventional Method (Synthesis of ITQ-2 Zeolite).
- MCM-22 (P) that had been prepared in the preceding section was delaminated by the literature method.
- an aqueous slurry of MCM-22 (P) (3.00 g, 20 wt% solid) was mixed with cetyltrimethylammonium bromide (Sigma Aldrich, -98%, 3.38 g), tetrapropylammonium hydroxide solution (Alfa Aesar, 40 wt%, 3.67 g), and the mixture was heated at 353 K (80°C) for 16 hours.
- tetrabutylammonium fluoride (Fluka, >90%, 1.92 g) and tetrabutylammonium chloride (Sigma Aldrich, 1.68 g) in deionized water (25.9 g). pH of the slurry was adjusted to approximately 9 by adding 40% tetrapropylammonium hydroxide solution, and the slurry was heated at 353 K (80°C) for 16 hours. After cooling the mixture, pH of the mixture was adjusted to approximately 2 by adding concentrated HCI aqueous solution in a fume hood. The mixture was transferred to a centrifuge bottle with screw cap, and quickly centrifuged to separate a solid from a solution. The supernatant solution was discarded carefully, and the remaining solid was dried at 313 K (40°C) overnight in the fume hood. The product yield was 90%.
- NMR shifts were reported in parts per million (ppm) when externally referenced to tetramethylsilane (TMS). See Figure 6C.
- Mercury porosimetry was conducted according to Standard Test Method for Determining Pore Volume Distribution of Catalysts by Mercury Intrusion Prolosimetry (ASTM D 428). See Figure 9, curve 3.
- ERB-1 was synthesized by the literature method. (Millini, et al, Microporous Materials, (1995) v. 4, p. 221). Sodium hydroxide (EMD Chemicals, 97%, 0.653 g) and piperidine (Sigma Aldrich, 99%, 6.360 g) were dissolved into deionized water (16.228 g). Boric acid (J.T. Baker, 4.396 g) was added to the mixture, and the whole mixture was stirred at 323 K until the boric acid was completely dissolved. After cooling down the solution to room temperature, fumed silica (Sigma Aldrich, 3.300 g) was added gradually over 1 hour.
- Example 1 After cooling the mixture, the pH of the mixture was adjusted to approximately 2 by adding concentrated HCI aqueous solution in a fume hood. The mixture was transferred to a centrifuge bottle with screw cap, and quickly centrifuged to separate the solids. The supernatant solution was discarded, and the solid was dried at 313 K (40°C) overnight. The product was then characterized as in Example 1. See Figure 12, pattern B.
- Figure 16 is a scanning electron microscopy image characterizing PREFER.
- Powder X-ray diffraction (XRD) patterns were collected on a Bruker D8 Advance diffractometer using a Cu Ka radiation. Transmission electron microscopy images were recorded on a JEOL JEM-2010 (200 kV). Argon gas adsorption isotherms were measured on a Micromeritics ASAP2020 at 86 K. Prior to measurement, samples were evacuated at 623 K for 4 h. 29 Si solid-state MAS NMR spectra were measured using a Bruker Avance 500 MHz spectrometer with a wide bore 1 1.7 T magnet and employing a Bruker 4 mm MAS probe.
- the spectral frequencies were 500.23 MHz for the 1H nucleus and 99.4 MHz for the 29 Si nucleus.
- 29 Si MAS NMRspectra were acquired after a 4 ⁇ 8-90 degree pulse with application of a strong X H decoupling pulse.
- the spinning rate was 12 kHz, and the recycle delay time was 300 s.
- Powder XRD (PXRD) characterizing UCB-3 shown in Figure 19 shows significant decrease and broadening of 200 peak (6.8°, 13 A) as compared with that of PREFER ( Figure 19) as PREFER is delaminated by the treatment.
- Argon gas physisorption isotherms of calcined materials are shown in Figure 20.
- Table 2 represent micropore volumes, external surface area, and total pore volumes.
- Powder XRD (PXRD) characterizing UCB-4 shown in Figure 21 shows disappearance of 200 peak (6.8°, 13 A) as compared with that of PREFER ( Figure 21) following the treatment described above.
- a distinctive advantage of UCB-4 relative to UCB-3 is a higher extent of delamination, as indicated by the complete absence of the (200) peak in Figure 21 (i.e. compare with intensity of this broad peak in Figure 19).
- UCB-4 Argon gas physisorption of calcined materials are shown in Figure 22.
- UCB-4 consists of a micropore volume that is less than 0.001 cm 3 /g, an external surface area of 171 m 2 /g, and a total pore volume of 0.51 cm 3 /g.
- a gel consisting of aluminum hydroxide (53wt% as A1203, 0.171 g), distilled water (6.88 g), diisobutylimidazolium hydroxide solution (0.50 mmol/g, 35.6 g), sodium hydroxide solution (IN, 8.89 g), and fumed silica (5.50 g) was divided into four portions. Each gel was heated in a 23 -mL Teflon-lined autoclave at 423 K with tumbling for 1 1 days. After the reaction mixtures were cooled down to room temperature, and the solid was separated by filtration, and subsequently washed with distilled water. The solid was dried at 353 K overnight. Synthesis and characterization of UCB-5 via delamination of Al-SSZ-70
- a mixture of Al-SSZ-70 (0.20 g), cetyltrimethylammonium bromide (CTAB, 0.22 g), tetrabutylammonium fluoride (TBAF, 0.34 g), tetrabutylammonium chloride (TBAC1, 0.34 g) in ⁇ , ⁇ -dimethyl formamide (4 mL) was heated in a sealed PFA tube at 373 K for 16 h. After cooling to room temperature, the slurry was subjected to sonication in an ice bath for 1 h. Then, the solid was separated by filtration, and washed with about 50 mL of DMF. After separation by filtration, the solid was dried at 323 K overnight.
- the synthesized material is designated as UCB-5.
- Powder XRD characterizing as-made Al-SSZ-70 and UCB-5 are shown in Figure 23.
- the pattern characterizing Al-SSZ-70 ( Figure 23a) shows a peak at 6.6° (13.4 A) that represents the lamellar structure of this material.
- the pattern for UCB-5 ( Figure 23b) shows complete disappearance of this peak, as layers in Al-SSZ-70 have become delaminated.
- a gel consisting of boric acid (0.172 g), distilled water (2.52 g),
- a mixture of B-SSZ-70 (0.20 g), cetyltrimethylammonium bromide (CTAB, 0.22 g), tetrabutylammonium fluoride (TBAF, 0.34 g), tetrabutylammonium chloride (TBAC1, 0.34 g) in ⁇ , ⁇ -dimethyl formamide (4 mL) was heated in a sealed PFA tube at 373 K for 16 h. After cooled to room temperature, the slurry was subjected to sonication in an ice bath for 1 h. Then, the solid was separated by filtration, and washed with about 50 mL of DMF. After separation by filtration, the solid was dried at 323 K overnight.
- the synthesized material is designated as UCB-6.
- Powder XRD characterizing as-made B-SSZ-70 and UCB-6 are shown in Figure 25.
- the pattern characterizing B-SSZ-70 ( Figure 25a) shows a peak at 6.6° (13.4 A) that represent lamellar structure of this material.
- the pattern for UCB-6 ( Figure 25b) shows a significant decrease and broadening of this peak, consistent with delaminated B- SSZ-70 layers.
- UCB-1 Approximately 30 mg of UCB-1 was calcined at 550 °C for 2 h in flowing dry nitrogen in thermogravimetric analyzer (TA Instruments, model TA2920). After cooling the calcined UCB-1 down to 150°C under the same dry nitrogen stream, 50 of pyridine base probe molecule was injected into the inlet gas flow line via syringe. The probe molecule adsorbed on acid sites of UCB-1. After the temperature was kept at 150°C for 30 h, the temperature of the sample was ramped up to 250 °C and held there for 2 h. Then, the temperature of the sample was ramped up to 350 °C and held there for 2 h. The same set of experiments was conducted with bulky pyridines such as 2,6-di-tert-butylpyridine (DTBP) and collidine.
- DTBP 2,6-di-tert-butylpyridine
- Figure 27 shows chemisorbed amounts of base molecules at 150-350°C. The results show that approximately 30-45% of acid sites accessible to pyridine are also accessible to DTBP or collidine. This large fraction of either DTBP- or collidine-accessible sites is due to the large fraction of acid sites near the external surface, as a result of delaminated layers in UCB-1.
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US13/161,091 US9522390B2 (en) | 2010-12-10 | 2011-06-15 | Oxide materials and synthesis by fluoride/chloride anion promoted exfoliation |
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US9296714B2 (en) * | 2012-02-07 | 2016-03-29 | Basf Se | Micropowder and molding containing a zeolitic material containing Ti and Zn |
RU2638851C2 (en) * | 2012-10-18 | 2017-12-18 | Басф Се | Post-treatment of deborated zeolite mww |
US9636669B2 (en) | 2013-02-22 | 2017-05-02 | The Regents Of The University Of California | Zeolitic materials with heteroatom substitutions on external surface of lattice framework |
US9126190B2 (en) * | 2013-07-30 | 2015-09-08 | Chevron U.S.A. Inc. | Zeolite SSZ-70 having enhanced external surface area |
WO2015066539A1 (en) | 2013-11-01 | 2015-05-07 | Chevron U.S.A. Inc. | Delaminated zeolite catalyzed aromatic alkylation |
JP6629304B2 (en) * | 2014-06-06 | 2020-01-15 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Synthesis of boron-containing zeolite having MWW framework structure |
WO2016040327A1 (en) | 2014-09-08 | 2016-03-17 | The Regents Of The University Of California | Highly active, selective, accessible, and robust zeolitic sn-baeyer-villiger oxidation catalyst |
US20160115397A1 (en) * | 2014-10-22 | 2016-04-28 | Chevron U.S.A. Inc. | Hydroprocessing of hydrocarbons using delaminated zeolite supports as catalysts |
US9738838B2 (en) * | 2014-10-22 | 2017-08-22 | Chevron U.S.A. Inc. | Hydroprocessing of hydrocarbons using delaminated zeolite supports as catalysts |
WO2016065035A1 (en) | 2014-10-22 | 2016-04-28 | Chevron U.S.A. Inc. | Hydrocarbon reactions using delaminated zeolite supports as catalysts |
US9783461B2 (en) * | 2014-11-04 | 2017-10-10 | Chevron U.S.A. Inc. | Olefin oligomerization using delaminated zeolite supports as catalyst |
US10253270B2 (en) * | 2014-11-04 | 2019-04-09 | Chevron U.S.A. Inc. | Alkylation reaction using delaminated zeolite supports as catalysts |
KR101685610B1 (en) * | 2015-02-16 | 2016-12-12 | 울산과학기술원 | Photocatalyst, method for manufacturing the same, and method for formation of hydrogen using the same |
GB201705241D0 (en) * | 2017-03-31 | 2017-05-17 | Johnson Matthey Catalysts (Germany) Gmbh | Catalyst composition |
KR20200121338A (en) | 2018-02-14 | 2020-10-23 | 셰브런 유.에스.에이.인크. | Exfoliated layered zeolite precursor and method of manufacturing it without ultrasonic treatment |
US11033886B2 (en) | 2019-02-27 | 2021-06-15 | Chevron U.S.A. Inc. | Molecular sieve SSZ-115, its synthesis and use |
KR102267465B1 (en) * | 2019-08-14 | 2021-06-22 | 고려대학교 산학협력단 | Method of Preparing Zeolite Nanosheets Via Simple Calcination Process and Particles Prepared Thereby |
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US7084087B2 (en) * | 1999-09-07 | 2006-08-01 | Abb Lummus Global Inc. | Zeolite composite, method for making and catalytic application thereof |
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US7122496B2 (en) * | 2003-05-01 | 2006-10-17 | Bp Corporation North America Inc. | Para-xylene selective adsorbent compositions and methods |
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